CN112390813B - Non-fullerene electron acceptor material and organic photovoltaic cell - Google Patents

Non-fullerene electron acceptor material and organic photovoltaic cell Download PDF

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CN112390813B
CN112390813B CN201910757583.5A CN201910757583A CN112390813B CN 112390813 B CN112390813 B CN 112390813B CN 201910757583 A CN201910757583 A CN 201910757583A CN 112390813 B CN112390813 B CN 112390813B
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electron acceptor
acceptor material
organic photovoltaic
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CN112390813A (en
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张纯凤
黄懿萱
李梓源
何嘉兴
庄子融
柯崇文
施宏旻
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Ways Technical Corp Ltd
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
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    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
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Abstract

A non-fullerene electron acceptor material of formula (I) and an organic photovoltaic cell having an active layer comprising the non-fullerene electron acceptor material. When the non-fullerene electron acceptor material is used as an electron acceptor, the energy conversion efficiency (PCE) of the organic photovoltaic cell can be effectively improved.

Description

Non-fullerene electron acceptor material and organic photovoltaic cell
Technical Field
The present invention relates to a non-fullerene electron acceptor material and an organic photovoltaic cell including the same, and more particularly, to a non-fullerene electron acceptor material of a thiophene (thiophene) bridged derivative having a multi-fused ring structure and an organic photovoltaic cell including the same.
Background
With the development of the times, the consumption of energy sources such as coal, oil, natural gas, nuclear energy and the like is gradually increased, and the energy crisis is gradually emerged. Solar power generation is a renewable and environmentally friendly power generation mode capable of reducing environmental pollution. The first generation of solar cells is a bulk of silicon crystal (silicon) solar cells, which have high photoelectric conversion efficiency. The second generation of solar cells is a thin-film type cadmium telluride (CdTe) solar cell, which has a large environmental pollution due to the toxicity of raw materials and the manufacturing method thereof. Third generation organic solar cells have been introduced, which include dye-sensitized solar cells (DSSC), nano-crystalline cells and organic photovoltaic cells (OPV). Compared with inorganic materials which need to be manufactured by vacuum process coating, the organic photovoltaic cell can be manufactured by methods such as dip coating, rotary coating, slit coating, screen printing, ink jet printing and the like, and low-cost and large-scale production is easier to realize. Among them, the organic photovoltaic cell of the new generation uses organic electron acceptor material in combination with conjugated polymer (electron donor material) as the material of the photovoltaic main absorption layer (active layer). The new generation of organic photovoltaic cells has several advantages: (1) the weight is light and the manufacturing cost is low; (2) has flexibility; (3) the designability of the device structure is strong; and (4) suitable for liquid phase processes (i.e., wet coating over large areas).
In addition to the aforementioned advantages, the diversity and development of the electron donor materials (conjugated polymers) in the active layer of the new generation of organic photovoltaic cells have led to the improvement of the energy conversion efficiency of the organic photovoltaic cells. However, most of the existing organic electron acceptor materials are mainly fullerene derivatives (such as PC60BM and PC70BM), and the compatibility with the electron donor material (conjugated polymer) is easily limited. In addition, the fullerene derivative itself has the disadvantages of easy dimerization under illumination, easy crystallization during heating, weak absorption in the visible light region, difficult structure modification and purification, high price and the like. Therefore, there is a need to develop an organic electron acceptor material that is not a fullerene derivative.
CN104557968B and CN105315298A disclose organic electron acceptor materials that are not fullerene derivatives, respectively, which can solve the disadvantages caused by using fullerene derivatives as electron acceptor materials. However, the energy conversion efficiency of the organic electron acceptor materials in the aforementioned patents is still low, and thus the requirements of the industry cannot be met.
Therefore, how to improve the structure of the existing organic electron acceptor material which is not a fullerene derivative, and further effectively improve the energy conversion efficiency (PCE) of the organic photovoltaic cell becomes a target of current research.
Disclosure of Invention
Accordingly, a first object of the present invention is to provide a non-fullerene electron acceptor material. When the non-fullerene electron acceptor material is used as an electron acceptor material, the energy conversion efficiency (PCE) of the organic photovoltaic cell can be effectively improved.
Accordingly, the non-fullerene electron acceptor material of the present invention refers to a thiophene (thiophene) bridged derivative having a multi-fused ring structure and substituted with halogen, and the non-fullerene electron acceptor material is represented by the following formula (I):
[ formula I ]]
Figure BDA0002169248690000021
Wherein the content of the first and second substances,
a is
Figure BDA0002169248690000031
Figure BDA0002169248690000041
Figure BDA0002169248690000051
B and C are each independently
Figure BDA0002169248690000052
X1-、X2、X3And X4Are each hydrogen, halogen or C1～C30Alkyl radical, and X1And X2At least one is halogen, X3And X4At least one is halogen;
y is NR5、O、S、Se、Si(R5)2Or C (R)5)2；
Z is O, S, Se or NR5；
R1Is hydrogen, halogen, C1～C30Alkyl radical, C1～C30Alkoxy radical, C1～C30Alkylaryl or C1～C30An alkyl heteroaryl group;
R2is hydrogen, halogen, C1～C30Alkyl or C1～C30An alkoxy group; and
R3、R4and R5Are each hydrogen or C1～C30An alkyl group.
Therefore, a second object of the present invention is to provide an organic photovoltaic cell. The organic photovoltaic cell of the present invention has a high energy conversion efficiency (PCE).
Thus, the organic photovoltaic cell of the present invention comprises an active layer. The active layer includes the non-fullerene electron acceptor material described above.
The invention has the following effects: the non-fullerene electron acceptor material is a core skeleton from three condensed rings to eleven condensed rings [ namely, A of the formula (I) ]]Linking a halogen-substituted thiophene as a bridging conjugated molecule [ i.e. X of formula (I) ]1And X2At least one is halogen, X3And X4At least one being halogen]And electron withdrawing groups [ i.e., B and C of the formula (I) ]are introduced at the terminal]. Therefore, when the non-fullerene electron acceptor material is used as an electron acceptor material, the material can absorb in a visible light region, and when the non-fullerene electron acceptor material is matched with an electron donor material (conjugated polymer), the non-fullerene electron acceptor material can have excellent photoelectric conversion characteristics. In other words, when the non-fullerene electron acceptor material is used as an electron acceptor material, the energy conversion efficiency (PCE) of the organic photovoltaic cell can be effectively improved.
The present invention will be described in detail below:
[ non-fullerene electron-acceptor material ]
The non-fullerene electron acceptor material of the present invention is represented by the formula (I).
It should be noted that, in the present invention, "alkylaryl", "alkylheteroaryl", "alkylphenyl" and "alkylthiophene" are respectively referred to as "peralkaneAryl substituted by a group, heteroaryl substituted by an alkyl group, phenyl substituted by an alkyl group and thiophene substituted by an alkyl group, wherein the alkylaryl, alkylheteroaryl, alkylphenyl and alkylthiophene may be substituted by other substituents (such as halogen) in addition to the alkyl group, and the "4-alkylphenyl" refers to phenyl substituted by an alkyl group at the para-position. The carbon number before "alkylaryl group", "alkylheteroaryl group", "alkylphenyl group" or "alkylthiophene" means the carbon number of an alkyl group, for example, C1～C30Alkylphenyl is denoted by C1～C30Alkyl-substituted phenyl. In addition, in the formula (I) of the present invention, each R of A and R is1May be the same or different substituents from each other.
Preferably, A in the formula (I) is
Figure BDA0002169248690000061
Figure BDA0002169248690000062
Wherein R is1Is hydrogen, halogen, C1～C30Alkyl radical, C1～C30Alkoxy radical, C1～C30Alkylaryl or C1～C30Alkyl heteroaryl, Y is NR5、O、S、Se、Si(R5)2Or C (R)5)2Z is O, S, Se or NR5，R5Is hydrogen or C1～C30An alkyl group.
More preferably, A is
Figure BDA0002169248690000071
R1Is C1～C30Alkyl or C1～C30An alkyl phenyl group. Still more preferably, R1Is C3～C13Alkyl or C1～C11An alkyl phenyl group. Still more preferably, R1Is C6～C10Alkyl or C4～C8An alkyl phenyl group. Still more preferably, the aforementioned alkylphenyl group is a 4-alkylphenyl group.
More preferably, A is
Figure BDA0002169248690000072
R1Is hydrogen, C1～C30Alkylphenyl or C1～C30An alkylthiophene. Still more preferably, R1Is hydrogen, C1～C11Alkylphenyl or C3～C13An alkylthiophene. Still more preferably, R1Is hydrogen, C4～C8Alkylphenyl or C6～C10An alkyl thiophene. Still more preferably, the aforementioned alkylphenyl group is a 4-alkylphenyl group. Still more preferably, the aforementioned alkylthiophenes are further substituted with a halogen.
More preferably, A is
Figure BDA0002169248690000073
R1Is hydrogen, Y is NR5Z is S, R5Is hydrogen or C1～C30An alkyl group. Still more preferably, R5Is C11～C21An alkyl group. Still more preferably, R5Is C14～C18An alkyl group.
Preferably, X in the formula (I)1-、X2、X3And X4Respectively hydrogen or halogen. More preferably, X1And X3Is halogen, X2And X4Is hydrogen.
Preferably, B and C in the formula (I) are respectively
Figure BDA0002169248690000074
Wherein R is2Is hydrogen or halogen.
[ organic photovoltaic cell ]
The organic photovoltaic cell of the present invention comprises an active layer comprising the aforementioned non-fullerene electron acceptor material.
Preferably, the active layer further comprises a conjugated polymer. More preferably, the weight ratio of the non-fullerene electron acceptor material to the conjugated polymer is in the range of 0.9 to 1.1.
Preferably, the organic photovoltaic cell further comprises an electron transport layer (electron transport layer), a hole transport layer (hole transport layer), a positive electrode and a negative electrode. The electron transport layer and the hole transport layer are respectively positioned on two opposite sides of the active layer, the cathode is positioned on one side of the electron transport layer opposite to the active layer, and the anode is positioned on one side of the hole transport layer opposite to the active layer. Preferably, the organic photovoltaic cell further comprises a substrate, wherein the substrate is located on a side of the negative electrode opposite to the electron transport layer.
The conjugated polymer is, for example, but not limited to, polymer 1 or polymer 2, wherein the specific structure of the polymer 1 comprises a repeating unit represented by the following formula (II), and the specific structure of the polymer 2 comprises a repeating unit represented by the following formula (III).
[ formula (II)]
Figure BDA0002169248690000081
[ formula (III)]
Figure BDA0002169248690000082
The material of the electron transport layer is, for example, but not limited to, zinc oxide (ZnO).
The material of the hole transport layer is, for example, but not limited to, molybdenum trioxide (MoO)3)。
The material of the cathode is, for example, but not limited to, Indium Tin Oxide (ITO).
The material of the positive electrode is, for example, but not limited to, silver.
The material of the substrate is, for example, but not limited to, glass.
Drawings
Other features and effects of the present invention will be apparent from the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a spectrum illustrating UV-VIS absorption spectra of non-fullerene electron acceptor materials of examples 1-6;
fig. 2 is a schematic view illustrating an organic photovoltaic cell to which example 1 is applied; and
FIG. 3 is a current-voltage graph illustrating the electrical properties of organic photovoltaic cells of application examples 1-6.
[ notation ] to show
70 substrate
80 negative electrode
91 electron transport layer
92 active layer
93 hole transport layer
100 positive electrode
Detailed Description
< example 1>
Preparation of non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 1 is shown in the following reaction scheme I.
[ reaction formula I ]
Figure BDA0002169248690000101
Compound 2
Figure BDA0002169248690000102
The preparation method of the compound 2 comprises the following steps:
3-chlorothiophene (compound 1) (10g,84.3mmol) was dissolved in 300mL of Tetrahydrofuran (THF). N-butyllithium (n-BuLi) (30.6mL,76.66mmol) was slowly added dropwise at-40 ℃ and stirred for 1 hour. Trimethyltin chloride (Me) is added3SnCl) (15.27g,76.66mmol), and the reaction was complete after 15 minutes of stirring back to room temperature (rt). Next, extraction was performed three times using n-heptane and water. The organic layer was extracted with saturated brine, dehydrated with anhydrous magnesium sulfate, and dried by suction with a rotary thickener to give Compound 2(18g, yield: 76%) as a yellow liquid.
Compound 4
Figure BDA0002169248690000111
A method for preparing compound 4:
1, 3-indandione (Compound 3) (4.4g,30mmol) and malononitrile (4.0g,60mmol) were dissolved in 44mL ethanol (EtOH). Sodium acetate (NaOAc) (3.2g,39.0mmol) was added and stirred at room temperature for three hours. Subsequently, an aqueous hydrochloric acid solution was added to acidify the reaction solution, and the resultant solid was filtered. The obtained solid was filtered, recrystallized from acetic acid, and vacuum-dried to obtain Compound 4(4g, yield: 70%) as a brown solid.
Compound 7
Figure BDA0002169248690000112
A method for preparing compound 7:
2, 5-Dibromoterephthalic acid (Compound 6) (500g,1.55mol) was mixed with 4L of methanol (MeOH) in a 10L round-bottomed flask. Slowly add sulfuric acid (H) in a water bath at 25 deg.C2SO4(ii) a 165mL,3.1 mol). Reflux (reflux) was heated overnight under nitrogen. After cooling, the solid was filtered, and then the solid was taken out and stirred overnight using a mixture of methanol and deionized water. After the solid was filtered and dried in vacuo, dimethyl 2, 5-dibromoterephthalate (compound 7) was obtained as a white solid (463g, yield: 85%).
Compound 8
Figure BDA0002169248690000121
A method for preparing compound 8:
methyl 2, 5-dibromoterephthalate (compound 7) (250g,0.71mol), 2-tributylstannyl thiophene (compound 5) (550g,1.5mol), tris (2-methylphenyl) phosphorus [ P (o-tol)3](21.6g,7.1mmol) and tris (dibenzylideneacetone) dipalladium [ Pd2(dba)3](19.2g,21mmol) was added to a 5L round-bottomed flask. Then 2.5L of tetrahydrofuran was added and heated to reflux under nitrogen for three hours. After cooling, methanol was added to give a solid, and the solid was filtered and dried in vacuo to give compound 8(231g, yield: 90%) as a green solid.
Compound 9
Figure BDA0002169248690000122
A method for preparing compound 9:
1-bromo-4-hexylbenzene (269g,1.11mol) was added to 1L of anhydrous tetrahydrofuran, and 2.5M n-butyllithium (n-BuLi) (335mL,0.84mol) was gradually added thereto at-78 ℃ and stirred at-78 ℃ for 1 hour. Then, Compound 8(50g,0.14mol) was added at-78 ℃ and slowly warmed to room temperature, followed by stirring for 1 hour. After the reaction was completed, 300mL of deionized water was added for extraction. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated in a rotary concentrator and then drained. Finally, purification was performed by silica gel column chromatography (dichloromethane: n-heptane ═ 1:1 as an eluent), and drying in vacuo afforded compound 9(92.5g, yield: 70%) as a brown solid.
Compound 10
Figure BDA0002169248690000131
A method of preparing compound 10:
compound 9(92.5g,98mmol) was added to 920mL of n-heptane (heptane) in a 2L round-bottomed flask. After the subsequent addition of 920mL of acetic acid (AcOH), 400mL of sulfuric acid (H) was slowly added2SO4) Dropped into a round-bottomed flask, and heated at 70 ℃ for 3 hours. After cooling, extraction was carried out with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then dried by suction using a rotary concentrator. Finally, purification was performed by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:1 as an eluent), and drying in vacuo gave compound 10(79g, yield: 88%) as pale yellow.
Compound 11
Figure BDA0002169248690000141
A method for preparing compound 11:
after adding compound 10(10g,11.02mmol) to 50mL of Tetrahydrofuran (THF), N-bromosuccinimide (NBS) (4.9g,27.6mmol) was added and the reaction was terminated at room temperature for 2 hours. The solvent was removed by concentration, and purified by silica gel column chromatography (n-heptane as a eluent), followed by vacuum drying, to give compound 11(9.4g, yield: 80%) as a pale yellow solid.
Compound 12
Figure BDA0002169248690000142
A method for preparing compound 12:
mixing compound 11(10g,9.39mmol), compound 2(6.6g,23.5mmol), tris (2-methylphenyl) phosphorus [ P (o-tol)3](0.29g,0.94mmol) and tris (dibenzylideneacetone) dipalladium [ Pd2(dba)3](0.26g 0.28mmol) was placed in a round-bottomed flask. Then 200mL of Tetrahydrofuran (THF) was added, heated to 65 ℃ under nitrogen and reacted for 7 hours. Then, the temperature was decreased, the solvent was removed by a rotary thickener, and the residue was purified by silica gel column chromatography (dichloromethane: n-heptane 1:1 as an eluent) to obtain compound 12(5.24g, yield: 49%) as a yellow solid.
Compound 13
Figure BDA0002169248690000151
A method for preparing compound 13:
after 20mL of Dichloroethane (DCE) and Dimethylformamide (DMF) (8.11mL,105.2mmol) were added to compound 12(10g,8.8mmol), phosphorus oxychloride (POCl) was slowly added dropwise in an ice bath3) (4.9mL,52.6 mmol). Then, the mixture was refluxed for 5 hours, cooled, added to an ice hydrochloric acid aqueous solution, extracted with dichloromethane, the organic layer was dehydrated with saturated anhydrous magnesium sulfate, the solvent was removed by a rotary concentrator, and purified by silica gel column chromatography (dichloromethane: n-heptane 1:1 as an eluent) to obtain a yellow solid compound 13(7.60g, yield: 72%).
Example 1
Figure BDA0002169248690000152
Preparation of example 1:
compound 13(1g,0.84mmol) and compound 8(0.81g,4.18mmol) are placed in a round bottom flask and 100mL chloroform (CHCl) is added3). Under nitrogen, 5mL pyridine (pyridine) was added. Then, the mixture was refluxed at 65 ℃ for 2 hours, cooled and the solvent was removed by a rotary thickener. Finally, purification by silica gel column chromatography (dichloromethane: n-heptane 2: 1 as eluent) gave the compound example 1 as a dark purple solid (0.85g, 65% yield).
< example 2>
Non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 2 is shown in the following reaction scheme II.
[ reaction formula II ]
Figure BDA0002169248690000161
Compound 14
Figure BDA0002169248690000162
A method of preparing compound 14:
compound 8(5g,13.9mmol) was added to 100mL of methanol (MeOH). Then, 6N aqueous sodium hydroxide (23.3mL,139.5mmol) was added, and the mixture was refluxed for 16 hours. After cooling, methanol was removed using rotary concentration. And acidifying with concentrated hydrochloric acid in an ice bath until the pH value is 1-2, and precipitating and filtering a white solid. After drying in vacuo, Compound 14 was obtained as a white solid (4.27g, yield: 93%).
Compound 15
Figure BDA0002169248690000171
A method of preparing compound 15:
the 2, 5-bis acid bithiophene (compound 14) (4g,12.1mmol) was mixed with 100mL Dichloromethane (DCM). Adding oxalyl chloride [ (COCl) -2](10.4mL,121.1mmol) with a few drops of Dimethylformamide (DMF). The ice bath was removed and the mixture was stirred back to room temperature for 16 hours, and dichloromethane and oxalyl chloride were removed using rotary concentration. Dichloromethane (200mL) was added to the reaction mixture in an ice bath, followed by aluminum trichloride (Al-Cl)3) (4.8g,36.3mmol) was added slowly to the reaction. Stirring was continued for 30 minutes in the ice bath, and the ice bath was removed and stirred back to room temperature for 4 hours. Finally, the reaction was poured into an aqueous hydrochloric acid solution, the solid was filtered, and dried under vacuum to give compound 15(2.78g, yield: 78%) as a dark blue solid.
Compound 16
Figure BDA0002169248690000172
A method of preparing compound 16:
compound 15(5g,17.0mmol) was mixed with 250mL diethylene glycol (diethylene glycol), and hydrazine hydrate (N) was added2H4·H2O) (6.8g,136mmol) and potassium hydroxide (19.1g,340mmol) are then heated to 160-170 ℃ for reaction for 24 hours. After cooling to room temperature, the reaction mixture was poured into an aqueous ice hydrochloric acid solution, and the filtered solid was rinsed with acetone and water and dried under vacuum to give compound 16 as a brown solid (2.5g, yield: 55%).
Compound 17
Figure BDA0002169248690000181
A method of preparing compound 17:
compound 16(1g,3.8mmol) was added to 50mL Tetrahydrofuran (THF). Potassium tert-butoxide (KOtBu) (4.2g,37.5mmol) and octyl bromide (C) were initially introduced in an ice bath8H17Br) (3.9mL,22.5mmol) was added dropwise to the reaction, and the ice bath was removed and stirred back to room temperature for 16 hours. Adding 50mL of water and 50mL of dichloromethane, washing for 2 times, drying with anhydrous magnesium sulfate, andthe solvent was removed by concentration. Finally, purification was carried out by silica gel column chromatography (using n-heptane as a eluent), followed by vacuum drying, whereby Compound 17(1.8g, yield: 67%) was obtained as a yellow solid.
Compound 18
Figure BDA0002169248690000182
A method of preparing compound 18:
compound 17(2g,2.8mmol) was added to 10mL Tetrahydrofuran (THF). N-bromosuccinimide (NBS) (1.1g,6.2mmol) was added under ice-bath and the ice-bath was removed and stirred back at room temperature for 2 hours. Then, the solvent was removed by concentration, and the residue was purified by silica gel column chromatography (using n-heptane as an eluent). After drying in vacuo, Compound 18 was obtained as a pale yellow solid (2.23g, yield: 92%).
Note that, the above references are referred to in j.am.chem.soc.,2010,132(33), pp 11437-11439.
Compound 19
Figure BDA0002169248690000191
A method of preparing compound 19:
the compound 18(3.0g,3.4mmol), the compound 23(2.4g,8.6mmol), tris (2-methylphenyl) phosphine [ P (o-tol) -3](103.5mg,0.3mmol) and tris (dibenzylideneacetone) dipalladium [ Pd2(dba)3](94.5mg,0.1mmol) was added to a round-bottomed flask. Subsequently, 90mL of Tetrahydrofuran (THF) was added and heated at reflux under nitrogen for 16 hours. After cooling, the tetrahydrofuran was removed using a rotary thickener and purified by silica gel column chromatography (n-heptane as the eluent). After drying in vacuo, Compound 19 was obtained as an orange oil (1.96g, yield: 60%).
Compound 20
Figure BDA0002169248690000192
A method of preparing compound 20:
compound 19(1.96g,2.1mmol) was added to 39mL of Dichloroethane (DCE) and Dimethylformamide (DMF) (9.6mL,124.2 mmol). Adding phosphorus oxychloride (POCl) under ice bath3) (5.8mL,62.1 mmol). The ice bath was then removed and heated to reflux for 16 hours. The mixture was cooled to room temperature, poured into an ice-hydrochloric acid aqueous solution, and extracted and washed 2 times with 50mL of dichloromethane. The extract was dried over anhydrous magnesium sulfate, concentrated to remove the solvent, and purified by silica gel column chromatography (n-heptane: chloroform: 1 as an eluent). After vacuum drying, Compound 20 was obtained as an orange solid (1.0g, yield: 48%).
Example 2
Figure BDA0002169248690000201
Preparation of example 2:
compound 20(1g,1.0mmol) and compound 4(970.9mg,5.0mmol) were added to 60mL of chloroform (CHCl)3). After addition of 1mL pyridine under nitrogen, the mixture was heated to reflux for 5 hours. After cooling, chloroform was removed using a rotary thickener and purified by silica gel column chromatography (n-heptane: chloroform: 1:4 as an eluent). After drying in vacuo, the compound of example 2(564mg, yield: 42%) was obtained as a dark brown solid.
< example 3>
Non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 3 is shown in the following reaction scheme III.
[ reaction formula III ]
Figure BDA0002169248690000202
Compound 22
Figure BDA0002169248690000211
A method of preparing compound 22:
5, 6-dichloro-1, 3-indandione (compound 21) (2g,9.3mmol) and malononitrile (1.23g,18.6mmol) were dissolved in 40mL of ethanol (EtOH). Sodium acetate (NaOAc) (1.14g,14mmol) was added and stirred at room temperature for 16 h. Subsequently, an aqueous hydrochloric acid solution was added to acidify the reaction solution, and the resultant solid was filtered. The solid was purified by silica gel column chromatography (dichloromethane as eluent) and dried under vacuum to give compound 22(1.94g, yield: 78%) as a brown solid.
Example 3
Figure BDA0002169248690000212
Preparation of example 3:
compound 13(500mg,0.4mmol) and compound 22(562.3mg,2.1mmol) were added to 50mL of chloroform (CHCl)3) After that, 1mL of pyridine (pyridine; py), heated to reflux for 3 hours. After cooling, chloroform was removed using a rotary thickener and purified by silica gel column chromatography (chloroform as the eluent). After drying in vacuo, the compound of example 3(590mg, yield: 83%) was obtained as a dark brown solid.
< example 4>
Non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 4 is shown in the following equation IV.
[ reaction formula IV ]
Figure BDA0002169248690000221
Compound 24
Figure BDA0002169248690000222
A method of preparing compound 24:
compound 23 can be prepared by the synthetic methods published in the document adv.mater.2017,29,1702125. After adding 50mL of tetrahydrofuran to compound 23(2g,1.42mmol), NBS (0.632g,3.55mmol) was added and the reaction was terminated at room temperature for 2 hours. The solvent was removed by concentration, purified by silica gel column chromatography (n-heptane as an eluent), and dried under vacuum to give compound 24(2.13g, yield: 96%) as a yellow solid.
Compound 25
Figure BDA0002169248690000231
A method of preparing compound 25:
mixing compound 24(2.13g,1.36mmol), compound 2(0.88g,3.128mmol), tris (2-methylphenyl) phosphorus [ P (o-tol)3](37mg,41mol) and Pd2(dba)3(41mg 0.136mmol) was placed in a round bottom flask, followed by addition of tetrahydrofuran (43mL), heating to 65 ℃ under nitrogen for 7 hours, cooling and removal of the solvent by a rotary concentrator. Finally, silica gel column chromatography (dichloromethane: n-heptane ═ 1: 7 as a eluent) was performed to obtain compound 25(1.95g, yield: 87%) as a yellow solid.
Compound 26
Figure BDA0002169248690000232
A method of preparing compound 26:
after adding compound 25(2g,1.22mmol) to Dichloroethane (DCE) (20mL) and Dimethylformamide (DMF) (3.4mL,38.156mmol), phosphorus oxychloride (POCl) was slowly added dropwise in an ice bath3) (5.64mL,76.2 mmol). Then, heating and refluxing for 4 hours, cooling, adding into ice hydrochloric acid aqueous solution, adding dichloromethane for extraction, removing water from the organic layer by using saturated anhydrous magnesium sulfate, and removing the solvent by using a rotary concentrator. Finally, purification was performed by silica gel column chromatography (dichloromethane: n-heptane 1:1 as a eluent) to obtain compound 26(1.31g, yield: 63%) as a yellow solid.
Example 4
Figure BDA0002169248690000241
Preparation of example 4:
compound 26(0.5g,0.30mmol) and compound 4(0.29g,1.47mmol) were placed in a round bottom flask and chloroform (50mL) was added, pyridine (2mL) was added under nitrogen, then refluxed at 65 ℃ for 2 hours, cooled and the solvent was removed by a rotary concentrator. Finally, purification by silica gel column chromatography (dichloromethane: n-heptane ═ 1:1 as eluent) gave a dark green solid compound, i.e., example 4(0.40g, yield: 66%).
< example 5>
Non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 5 is shown in the following equation V.
[ reaction formula V ]
Figure BDA0002169248690000251
Compound 28
Figure BDA0002169248690000252
Preparation of compound 28:
compound 27 can be prepared by the synthetic methods published in the document adv.mater.2017,29,1702125. After adding 10mL of tetrahydrofuran to compound 27(1.5g,1.02mmol), NBS (0.45g,2.54mmol) was added and the reaction was terminated at room temperature for 2 hours. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (n-heptane as an eluent) and dried under vacuum to give compound 28(1.55g, yield: 93%) as a yellow solid.
Compound 29
Figure BDA0002169248690000261
A method of preparing compound 29:
compound 28(3.5g,2.14mmol), compound 2(1.4g,4.92mmol), tris (2-methylphenyl) phosphorus (65mg,0.21mmol) and Pd2(dba)3(59mg,0.06mmol) was put into a round-bottomed flask, followed by addition of tetrahydrofuran (70mL), heating to 65 ℃ under nitrogen protection for 7 hours, cooling and solvent removal by a rotary concentrator, and purification by silica gel column chromatography (dichloromethane: n-heptane ═ 1: 9 as an extract) gave compound 29(3.3g, yield: 90%) as a yellow solid.
Compound 30
Figure BDA0002169248690000262
A method of preparing compound 30:
after adding dichloroethane (30mL) and dimethylformamide (8.11mL,105.24mmol) to compound 29(3g,1.754mmol), phosphorus oxychloride (POCl) was slowly added dropwise in an ice bath3) (4.9mL,52.62mmol), heating to reflux for 4 hours, cooling, adding into ice hydrochloric acid aqueous solution, adding dichloromethane for extraction, removing water from the organic layer with saturated anhydrous magnesium sulfate, and removing the solvent with a rotary concentrator. Finally, purification was performed by silica gel column chromatography (dichloromethane: n-heptane 3: 2 as an eluent) to obtain compound 30(2.11g, yield: 68%) as a yellow solid.
Example 5
Figure BDA0002169248690000271
Preparation of example 5:
compound 30(0.5g,0.28mmol) and compound 4(0.27g,1.41mmol) were placed in a round bottom flask and chloroform (50mL) was added, pyridine (2mL) was added under nitrogen, followed by reflux at 65 ℃ for 2 hours, cooling and solvent removal by a rotary concentrator, and purification by silica gel column chromatography (dichloromethane: n-heptane ═ 1:1 as eluent) gave a dark green solid compound, i.e., example 5(0.37g, yield: 61%).
< example 6>
Non-fullerene electron acceptor materials
The procedure for the preparation of the non-fullerene electron acceptor material of example 6 is shown in the following equation VI.
[ reaction formula VI ]
Figure BDA0002169248690000281
Compound 32
Figure BDA0002169248690000282
A method of preparing compound 32:
in a 500mL round-bottom flask, 4, 7-dibromo-5, 6-dinitrobenzothiadiazole (compound 31) (20g,52.1mmol), 2-tributylstannyl thiophene (compound 5) (42.7g,115mmol), tris (2-furyl) phosphine (1.58g,5.21mmol), and Pd2(dba)3(1.43g,1.56mmol) was dissolved in 200mL tetrahydrofuran, sulfuric acid (165mL,3.1mol) was slowly added to the water bath at 25 deg.C and heated at reflux under nitrogen for two hours. After cooling, the solid was filtered, collected and dried under vacuum to give Compound 32(18.5g, yield: 91%) as a red solid.
Compound 33
Figure BDA0002169248690000291
A method of preparing compound 33:
compound 32(18.5g,47.3mmol), triphenylphosphine (99g,37.8mmol) were added to a 500mL round bottom flask, followed by 200mL o-dichlorobenzene (ODCB), and heated under reflux for 12 hours under nitrogen. After cooling, heptane was added to give a solid, and the solid was filtered and dried in vacuo to give compound 33(15g, yield: 99%) as a yellow solid.
Compound 34
Figure BDA0002169248690000292
A method of preparing compound 34:
in a 250mL round bottom flask, compound 33(6g,18.4mmol), 1-iodo-2-hexyldecane (32.4g,92mmol) were dissolved in 60mL Dimethylformamide (DMF), sodium hydroxide (5.9g,14.7mmol) was slowly added, and the mixture was heated at 50 ℃ under nitrogen reflux for two hours. After the reaction, 300mL of ethyl acetate and 300mL of deionized water were added for extraction. The organic layer was dried over anhydrous magnesium sulfate and filtered, then concentrated and drained by a rotary concentrator, and then purified by silica gel column chromatography (petroleum ether/dichloromethane), to obtain compound 34(8.75g, yield: 61%) as a brown oil after vacuum drying.
Compound 35
Figure BDA0002169248690000301
A method of preparing compound 35:
in a 100mL round bottom flask, compound 34(9.5g,12.3mmol) was dissolved in 30mL tetrahydrofuran, and sodium N-bromosuccinimide (4.58g,25.7mmol) was added slowly and stirred under nitrogen at room temperature for 20 min. After the reaction was complete, 50mL of ethyl acetate and 50mL of deionized water were added for extraction. The organic layer was dried over anhydrous magnesium sulfate and filtered, then concentrated and drained by a rotary concentrator, and then purified by silica gel column chromatography (petroleum ether/dichloromethane) to obtain compound 35(9.56g, yield: 84%) as a brown oil after vacuum drying.
Compound 36
Figure BDA0002169248690000302
A method of preparing compound 36:
in a 250mL round-bottom flask, compound 35(6.3g,0.68mmol), 2-tributylstannyl-3-chlorothiophene (4g,1.43mmol), tris (2-furyl) phosphine (62.7mg,6.78mmol) and Pd2(dba)3(186mg,0.02mmol) was dissolved in 100mL of tetrahydrofuranAnd heating and refluxing for 16 hours under the protection of nitrogen. After the reaction, the reaction mixture was concentrated and dried by a rotary concentrator, purified by silica gel column chromatography (petroleum ether/dichloromethane), and dried in vacuo to obtain compound 36(2.87g, yield: 42%) as a red oily substance.
Compound 37
Figure BDA0002169248690000311
A method of preparing compound 37:
in a 100mL round-bottom flask, compound 36(2.87g,0.28mmol) and anhydrous Dimethylformamide (DMF) (13mL,17mmol) were added dissolved in 60mL 1, 2-dichloroethane. Slowly adding phosphorus oxychloride (POCl) in ice bath3) (5.3mL,5.7mol), then slowly heated to reflux and stirred for 16 h. After the reaction was completed, dichloromethane was added for extraction. The organic layer was dried and filtered over anhydrous magnesium sulfate, concentrated and drained by a rotary concentrator, purified by silica gel column chromatography (petroleum ether/dichloromethane), and dried under vacuum to obtain compound 37(1.8g, yield: 59%) as a red solid.
Example 6
Figure BDA0002169248690000312
Preparation of example 6:
compound 37(1g,0.09mmol) and compound 4(0.73g,0.37mmol) were added to a 250mL round-bottomed flask, followed by addition of 100mL of chloroform for dissolution, followed by slow dropwise addition of 2mL of pyridine, and heating and refluxing under nitrogen for 5 hours. After the reaction, the reaction mixture was cooled, concentrated and dried by a rotary concentrator, and then a solid was precipitated with methanol, and finally purified by silica gel column chromatography (petroleum ether/chloroform), and the resulting product was dried under vacuum to obtain a deep blue solid compound, i.e., example 6(1.1g, yield: 82%).
Referring to the spectrum of FIG. 1, FIG. 1 illustrates the UV-VIS absorption spectra of the non-fullerene electron acceptor materials of examples 1-6.
< application example 1>
Organic photovoltaic cell
Referring to fig. 2, an organic photovoltaic cell of an application example 1 is shown. The organic photovoltaic cell includes an active layer 92, an electron transport layer 91, a hole transport layer 93, a cathode 80, an anode 100, and a substrate 70.
The electron transport layer 91 and the hole transport layer 93 are respectively located on two opposite sides of the active layer 92. The cathode 80 is located on the side of the electron transport layer 91 opposite to the active layer 92, and the anode 100 is located on the side of the hole transport layer 93 opposite to the active layer 92. The substrate 70 is located on a side of the cathode 80 opposite to the electron transport layer 91.
In this particular application example, the active layer 92 includes the non-fullerene electron acceptor material of example 1 (as the electron acceptor material) and the conjugated polymer 1 (as the electron donor material), and the weight ratio of the non-fullerene electron acceptor material of example 1 to the conjugated polymer 1 is 1. The material of the electron transport layer 91 is zinc oxide (ZnO). The hole transport layer 93 is made of molybdenum trioxide (MoO)3). The material of the cathode 80 is Indium Tin Oxide (ITO). The material of the positive electrode 100 is silver. The substrate 70 is made of glass.
The following description of the method for manufacturing the organic photovoltaic cell according to application example 1 is made with reference to fig. 2:
step (1) -preparation of the glass substrate 70 and the negative electrode 80: the patterned Indium Tin Oxide (ITO) glass substrate (12 Ω/□) was sequentially cleaned in an ultrasonic oscillation tank with a detergent, deionized water, acetone, and isopropyl alcohol for 10 minutes. The ITO glass substrate was cleaned by ultrasonic oscillation and then surface-treated in an ultraviolet ozone (UV-ozone) cleaner for 30 minutes. Wherein, the glass substrate is the substrate 70, and the ITO is the cathode 80.
Step (2) -preparation of the electron transport layer 91: reacting diethyl zinc (ZnEt)2) The solution is spin-coated on the ITO glass substrate treated in step (1), and baked in a glove box at 120 ℃ for 20 minutes to form a ZnO layer (i.e., the electron transport layer 91) on the negative electrode 80.
Step (3) -preparation of active layer 92: the non-fullerene electron acceptor material of example 1 was mixed with conjugated polymer 1 (weight ratio 1: 1) and prepared into an active layer solution using chlorobenzene as a solvent. The active layer solution was spin-coated on the electron transport layer 91 and baked at a temperature of 100 ℃ for 10 minutes in a nitrogen atmosphere to form the active layer 92.
Step (4) -preparation of hole transport layer 93: and (4) conveying the semi-finished product obtained in the step (3) into a vacuum cavity. Next, molybdenum trioxide (MoO) of about 4nm was deposited by heating3) The hole transport layer 93 is formed on the active layer 92.
Step (5) -preparation of the positive electrode 100: silver of about 100nm is thermally deposited on the electrokinetic transport layer 93 to form the positive electrode 100.
< application examples 2 to 6>
Organic photovoltaic cell
The organic photovoltaic cell structures and the manufacturing methods of application examples 2 to 6 are similar to those of application example 1, and the differences are that the electron acceptor material used in the active layer 92 of application examples 2 to 6 and the conjugated polymer used in the active layer 92 of application example 3 are different from those of application example 1. The electron acceptor materials and conjugated polymers used in application examples 1 to 6 are collated in Table 1 below.
TABLE 1
Electron acceptor materials in active layers Conjugated polymers
Application example 1 Non-fullerene electron acceptor material of example 1 Polymer 1
Application example 2 Non-fullerene electron acceptor material of example 2 Polymer 1
Application example 3 Non-fullerene electron acceptor material of example 3 Polymer 2
Application example 4 Non-fullerene electron acceptor material of example 4 Polymer 1
Application example 5 Non-fullerene electron acceptor material of example 5 Polymer 1
Application example 6 Non-fullerene electron acceptor material of example 6 Polymer 1
< analysis of Electrical Properties of organic photovoltaic cell >
The measurement area of the organic photovoltaic cell of application examples 1-6 is defined as 0.04cm by the metal mask2. The electrical test was performed using a multifunctional power meter (manufacturer model: Keithley 2400) as a power supply and controlled by a Lab-View computer program. The organic photovoltaic cell was irradiated with simulated sunlight using a solar light source simulator (model name: SAN-EI XES-40S3) and recorded in a computer program. The resulting current-voltage curve is shown in fig. 3. Wherein the illuminance of the simulated sunlight is 100mW/cm2(AM1.5G)。
< analysis of energy conversion efficiency (PCE) of organic photovoltaic cell >
The active layer materials used in the organic photovoltaic cells of application examples 1 to 6, as well as the open circuit voltage (Voc), the short-circuit current (Jsc), the Fill Factor (FF) and the energy conversion efficiency (PCE) thereof are summarized in table 2 below. The open-circuit voltage (Voc) and the short-circuit current (Jsc) are the intercepts of the current-voltage curves of fig. 3 on the X-axis (open-circuit voltage) and the Y-axis (short-circuit current), respectively. The Fill Factor (FF) is the area that can be plotted within the current-voltage curve of fig. 3 divided by the product of the short circuit current and the open circuit voltage. The energy conversion efficiency (PCE) is the product of the open circuit voltage, short circuit current and fill factor divided by the amount of the simulated solar energy illuminated, and is better the higher the value.
TABLE 2
Figure BDA0002169248690000341
From the results in table 2, it can be found that the organic photovoltaic cells of application examples 1 to 6 all have good energy conversion efficiency (PCE), and therefore, from the above results, it can be known that the energy conversion efficiency (PCE) of the organic photovoltaic cell can be effectively improved when the non-fullerene electron acceptor material of the present invention is used as an electron acceptor material. In particular, the electron acceptor material of example 1 also performed best when a different electron acceptor material was changed.
As described above, the non-fullerene electron acceptor material of the present invention has a core skeleton of three to eleven fused rings [ i.e., A of formula (I) ]]Linking a halogen-substituted thiophene as a bridging conjugated molecule [ i.e. X of formula (I) ]1And X2At least one is halogen, X3And X4At least one being halogen]And electron-withdrawing groups [ i.e. B and C of formula (I) ]are introduced at the terminal]. Therefore, when the non-fullerene electron acceptor material is used as an electron acceptor material, the material can have high-intensity absorption in a visible light region, and when the non-fullerene electron acceptor material is matched with an electron donor material (conjugated polymer), the non-fullerene electron acceptor material can have excellent photoelectric conversion characteristics. In other words, the non-fullerene of the present inventionWhen the alkene electron acceptor material is used as the electron acceptor material, the energy conversion efficiency (PCE) of the organic photovoltaic cell can be effectively improved, so that the aim of the invention can be really achieved.
However, the above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all simple equivalent changes and modifications made according to the claims and the contents of the patent specification are still included in the scope of the present invention.

Claims (4)

1. A non-fullerene electron acceptor material represented by the following formula (I):
[ formula (I)]
Figure FDA0003509997210000011
Wherein, the first and the second end of the pipe are connected with each other,
a is
Figure FDA0003509997210000012
B and C are each independently
Figure FDA0003509997210000013
X1And X3Is halogen, X2And X4Is hydrogen;
y is NR5；
Z is S;
R1is hydrogen;
R2is hydrogen or halogen; and
R5is C1～C30An alkyl group.
2. An organic photovoltaic cell comprising an active layer comprising the non-fullerene electron acceptor material of claim 1.
3. The organic photovoltaic cell of claim 2, wherein the active layer further comprises a conjugated polymer.
4. The organic photovoltaic cell of claim 3, further comprising an electron transport layer, a hole transport layer, a positive electrode, and a negative electrode, wherein the electron transport layer and the hole transport layer are respectively disposed on opposite sides of the active layer, the negative electrode is disposed on a side of the electron transport layer opposite to the active layer, and the positive electrode is disposed on a side of the hole transport layer opposite to the active layer.
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